Shampoo compositions

ABSTRACT

The conditioning performance of small particle size emulsified silicone in a surfactant-based shampoo composition can be significantly boosted by the inclusion in the shampoo composition of an amino functionalized silicone. Accordingly, the invention provides an aqueous shampoo composition comprising, in addition to water:  
     i) at least one surfactant chosen from anionic, nonionic, zwitterionic or amphoteric surfactants or mixtures thereof;  
     ii) an amino functionalized silicone; and  
     iii) emulsified particles of an insoluble, non-amino functionalized silicone, in which the average silicone particle size of the emulsified non-amino functional silicone in the shampoo composition is less than 2 microns.

FIELD OF THE INVENTION

1. This invention relates to shampoo compositions, and more particularlyto shampoo compositions containing emulsified particles of silicone,which compositions condition the hair leaving it softer and moremanageable.

BACKGROUND AND PRIOR ART

2. The use of silicones as conditioning agents in cosmetic formulationsis well known and widely documented in the patent literature. Generally,dispersed droplets of the silicone oil are suspended in the composition,which is then applied to the hair to deposit the silicone material onthe hair shaft.

3. A typical method of silicone shampoo manufacture is disclosed in WO92/10162. Essentially, the silicone material is emulsified directly intothe shampoo by an in situ hot process, in which the complete shampoomixture incorporating the silicone is mixed thoroughly at elevatedtemperature, pumped through a high shear mill and then cooled. Thesilicone can be dispersed in a first process stage with anionicsurfactant and fatty alcohol to form a premix. The premix is then mixedwith the remaining materials of the shampoo, pumped through a high shearmill, and cooled to obtain the final composition.

4. A disadvantage associated with an in situ hot process such as isdescribed in WO 92/10162 is that factory handling of viscous siliconeoil is difficult in the context of a full shampoo manufacturingoperation.

5. A further disadvantage is that special equipment is normally neededto control silicone particle size during manufacture. GB 2 170 216 Adiscloses a similar process, in which the full shampoo compositionincorporating insoluble, nonvolatile silicone is sheared with a highshear mixer until the silicone particles are on average less than 2microns in diameter. The particle size distribution is then said to befrom about 2 to about 55 microns.

6. In order to solve the above mentioned problems with in situ hotprocessing of silicone, the alternative of incorporating the silicone asa preformed aqueous emulsion has been proposed. Such a method has theconsequences that the silicone is incorporated with a predeterminable,controllable particle size distribution. The silicone is insoluble andremains emulsified in the fully formulated shampoo composition, and thusthe step of high shear processing of the silicone within the fullyformulated shampoo composition is not required. This also makesmanufacture of the compositions easier.

7. A typical method for incorporating insoluble, non-volatile siliconematerials into a conditioning shampoo is disclosed in U.S. Pat. No.5,085,857 in which such materials are incorporated in the shampoocomposition as a pre-formed aqueous emulsion of average particle sizeless than 2 microns. All the ingredients are mixed in a simple hot orcold process in which the average particle size of the silicone materialin the emulsion remains the same in the final shampoo composition.Preferably, this size is from 0.01 to 1 micron, e.g. 0.4 micron.

8. EP 0 529 883 A1 discloses hair shampoo compositions made by anequivalent method and comprising microemulsified particles of siliconehaving a particle size of 0.15 microns or less, e.g., 0.036 microns.Reducing the silicone particle size still further in this way is said toimprove stability, optical properties and conditioning performance.

9. A problem encountered with these small particle size siliconeformulations is that the conditioning performance may be insufficientfor many people, particularly in regions such as Japan and South EastAsia where consumers desire a high level of conditioning and a “weighty”feel to their hair.

10. We have now found that the conditioning performance of smallparticle size emulsified silicone in a surfactant-based shampoocomposition can be significantly boosted by the inclusion in the shampoocomposition of an amino functionalised silicone.

11. U.S. Pat. No. 5,198,209 (Amway Corp) and L'Oreal EP 0 811 371disclose conditioning shampoos with cleansing surfactant and acombination of dimethicone and trimethylsilylamodimethicone. Theexemplified compositions use dimethicone fluid such as DC200 (60,000cst). The dimethicone fluid is added directly to the shampoo as neatsilicone oil of unspecified silicone particle size.

SUMMARY OF THE INVENTION

12. The invention provides an aqueous shampoo composition comprising, inaddition to water:

13. i) at least one surfactant chosen from anionic, nonionic,zwitterionic or amphoteric surfactants or mixtures thereof;

14. ii) an amino functionalised silicone; and

15. iii) emulsified particles of an insoluble, non-amino functionalisedsilicone, in which the average silicone particle size of the emulsifiednon-amino functional silicone in the shampoo composition is less than 2microns.

DETAILED DESCRIPTION OF THE INVENTION

16. Surfactant

17. The composition according to the invention comprises a surfactantchosen from anionic, nonionic, zwitterionic or amphoteric surfactants ormixtures thereof.

18. Suitable anionic surfactants include the alkyl sulphates, alkylether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkylsuccinates, alkyl sulphosuccinates, N-alkoyl sarcosinates, alkylphosphates, alkyl ether phosphates, alkyl ether carboxylates, andalpha-olefin sulphonates, especially their sodium, magnesium ammoniumand mono-, di- and triethanolamine salts. The alkyl and acyl groupsgenerally contain from 8 to 18 carbon atoms and may be unsaturated. Thealkyl ether sulphates, alkyl ether phosphates and alkyl ethercarboxylates may contain from one to 10 ethylene oxide or propyleneoxide units per molecule, and preferably contain 2 to 3 ethylene oxideunits per molecule.

19. Examples of suitable anionic surfactants include sodium oleylsuccinate, ammonium lauryl sulphosuccinate, ammonium lauryl sulphate,sodium dodecylbenzene sulphonate, triethanolamine dodecylbenzenesulphonate, sodium cocoyl isethionate, sodium lauroyl isethionate andsodium N-lauryl sarcosinate. The most preferred anionic surfactants aresodium lauryl sulphate, triethanolamine lauryl sulphate, triethanolaminemonolauryl phosphate, sodium lauryl ether sulphate 1EO, 2EO and 3EO,ammonium lauryl sulphate and ammonium lauryl ether sulphate 1EO, 2EO and3EO.

20. Nonionic surfactants suitable for use in compositions of theinvention may include condensation products of aliphatic (C₈-C₁₈)primary or secondary linear or branched chain alcohols or phenols withalkylene oxides, usually ethylene oxide and generally having from 6 to30 ethylene oxide groups. Other suitable nonionics include mono- ordi-alkyl alkanolamides. Example include coco mono- or di- ethanolamideand coco mono-isopropanolamide.

21. Amphoteric and zwitterionic surfactants suitable for use incompositions of the invention may include alkyl amine oxides, alkylbetaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines),alkyl glycinates, alkyl carboxyglycinates, alkyl amphopropionates,alkylamphoglycinates alkyl amidopropyl hydroxysultaines, acyl tauratesand acyl glutamates, wherein the alkyl and acyl groups have from 8 to 19carbon atoms. Examples include lauryl amine oxide, cocodimethylsulphopropyl betaine and preferably lauryl betaine, cocamidopropylbetaine and sodium cocamphopropionate.

22. Generally, the surfactants are present in shampoo compositions ofthe invention in an amount of from 0.1 to 50%, preferably from 5 to 30%,more preferably from 10% to 25% by weight.

23. Amino functionalised silicone

24. By “amino functionalised silicone” is meant a silicone containing atleast one primary, secondary or tertiary amine group, or a quaternaryammonium group.

25. Examples include:

26. (i) polysiloxanes having the CTFA designation “amodimethicone”, andthe general formula:

HO—[Si(CH₃)₂—O—]_(x)—[Si(OH)(CH₂CH₂CH₂—NH—CH₂CH₂NH₂)—O—]_(y)—H

27. in which x and y are numbers depending on the molecular weight ofthe polymer, generally such that the molecular weight is between about5,000 and 500,000.

28. (ii) polysiloxanes having the general formula:

R′_(a)G_(3−a)—Si(OSiG₂)_(n)—(OSiG_(b)R′_(2−b))_(m)—O—SiG_(3−a)R′_(a)

29. in which:

30. G is selected from H, phenyl, OH or C₁₋₈ alkyl, e.g. methyl;

31. a is 0 or an integer from 1 to 3, preferably 0;

32. b is 0 or 1, preferably 1;

33. m and n are numbers such that (m+n) can range from 1 to 2000,preferably from 50 to 150;

34. m is a number from 1 to 2000, preferably from 1 to 10;

35. n is a number from 0 to 1999, preferably from 49 to 149, and

36. R′ is a monovalent radical of formula —C_(q)H_(2q)L in which q is anumber from 2 to 8 and L is an aminofunctional group selected from thefollowing:

37. —NR″—CH₂—CH₂—N(R″)₂

38. —N(R″)₂

39. —N⁺(R″)₃A⁻

40. —N⁺H(R″)₂A⁻

41. —N⁺H(R″)A⁻

42. —N(R″)—CH₂—CH₂—N⁺H₂(R″)A⁻

43. which R″ is selected from H, phenyl, benzyl, or a saturatedmonovalent hydrocarbon radical, e.g. C₁₋₂₀ alkyl, and

44. A is a halide ion, e.g. chloride or bromide.

45. Suitable amino functionalised silicones corresponding to the aboveformula include those polysiloxanes termed“trimethylsilylamodimethicone” as depicted below, and which aresufficiently water insoluble so as to be useful in compositions of theinvention:

Si(CH₃)₃—O—[Si(CH₃)₂—O—]_(x)—[Si(CH₃) (R—NH—CH₂CH₂NH₂)—O—]_(y)—Si (CH₃)₃

46. wherein x+y is a number from about 50 to about 500, and wherein R isan alkylene group having from 2 to 5 carbon atoms. Preferably, thenumber x+y is in the range of from about 100 to about 300.

47. (iii) quaternary silicone polymers having the general formula:

{(R¹) (R²) (R³) N⁺CH₂CH(OH)CH₂O(CH₂)₃[Si(R⁴)(R⁵)—O—]_(n)—Si(R⁶)(R⁷)—(CH₂)₃—O—CH₂CH(OH)CH₂N⁺(R⁸) (R⁹) (R¹⁰)}(X⁻)₂

48. wherein R¹ and R¹⁰ may be the same or different and may beindependently selected from H, saturated or unsaturated long or shortchain alk(en)yl, branched chain alk(en)yl and C₅-C₈ cyclic ring systems;

49. R² thru' R⁹ may be the same or different and may be independentlyselected from H, straight or branched chain lower alk(en)yl, and C₅-C₈cyclic ring systems;

50. n is a number within the range of about 60 to about 120, preferablyabout 80, and

51. X⁻is preferably acetate, but may instead be for example halide,organic carboxylate, organic sulphonate or the like.

52. Suitable quaternary silicone polymers of this class are described inEP-A-0 530 974.

53. Amino functional silicones suitable for use in the invention willtypically have a mole % amine functionality in the range of from about0.1 to about 8.0 mole %, preferably from about 0.1 to about 5.0 mole %,most preferably from about 0.1 to about 2.0 mole %. In general the amineconcentration should not exceed about 8.0 mole % since we have foundthat too high an amine concentration can be detrimental to totalsilicone deposition and therefore conditioning performance.

54. The viscosity of the amino functional silicone is not particularlycritical and can suitably range from about 100 to about 500,000 cst.

55. Specific examples of amino functional silicones suitable for use inthe invention are the aminosilicone oils DC2-8220, DC2-8166, DC2-8466,and DC2-8950-114 (all ex Dow Corning), and GE 1149-75, (ex GeneralElectric Silicones).

56. Also suitable are emulsions of amino functional silicone oils withnon ionic and/or cationic surfactant.

57. Suitably such pre-formed emulsions will have an average aminofunctional silicone particle size in the shampoo composition of lessthan 30, preferably less than 20, more preferably less than 10 microns.We have found that reducing the particle size generally improvesconditioning performance. Most preferably the average amino functionalsilicone particle size is less than 2 microns, ideally it ranges from0.01 to 1 micron. Silicone emulsions having an average silicone particlesize of ≦0.15 microns are generally termed microemulsions.

58. Particle size may be measured by means of a laser light scatteringtechnique, using a 2600D Particle Sizer from Malvern Instruments.

59. Pre-formed emulsions of amino functionalised silicone are availablefrom suppliers of silicone oils such as Dow Corning and GeneralElectric. Specific examples include DC929 Cationic Emulsion, DC939Cationic Emulsion, DC949 Cationic Emulsion, and the non-ionic emulsionsDC2-7224, DC2-8467 and DC2-8154 (all ex Dow Corning).

60. An example of a quaternary silicone polymer useful in the presentinvention is the material K3474, ex Goldschmidt.

61. Emulsified, non-amino functionalised silicone

62. The shampoo composition of the invention comprises a non-aminofunctionalised silicone. The silicone is insoluble in the aqueous matrixof the shampoo composition and so is present in an emulsified form, withthe silicone present as dispersed particles.

63. The average silicone particle size of the emulsified non-aminofunctional silicone in the shampoo composition is less than 2 microns.Ideally it ranges from 0.01 to 1 micron. We have found that reducing theparticle size in this way improves the overall conditioning performancefrom the shampoo composition. Particle size may be measured by means ofa laser light scattering technique, using a 2600D Particle Sizer fromMalvern Instruments.

64. Suitable silicones include polydiorganosiloxanes, in particularpolydimethylsiloxanes which have the CTFA designation dimethicone. Alsosuitable for use in shampoo compositions of the invention arepolydimethyl siloxanes having hydroxyl end groups, which have the CTFAdesignation dimethiconol. Also suitable for use in shampoos of theinvention are silicone gums having a slight degree of cross-linking, asare described for example in WO 96/31188. These materials can impartbody, volume and stylability to hair, as well as good wet and dryconditioning.

65. Various methods of making emulsions of particles of silicones foruse in the invention are available and are well known and documented inthe art. For example, emulsions may be prepared by high shear mechanicalmixing of the silicone and water, or by emulsifying the silicone withwater and an emulsifier (mixing the silicone into a heated solution ofthe emulsifier for instance), or by a combination of mechanical andchemical emulsification. A further suitable technique for preparation ofemulsions of particles of silicones is emulsion polymerisation. Emulsionpolymerised silicones as such are described in U.S. Pat. No. 2,891,820(Hyde), U.S. Pat. No. 3,294,725 (Findlay) and U.S. Pat. No. 3,360,491(Axon).

66. Suitable silicone emulsions for use in the invention arecommercially available in a pre-emulsified form. This is particularlypreferred since the pre-formed emulsion can be incorporated into theshampoo composition by simple mixing. Pre-formed emulsions are availablefrom suppliers of silicone oils such as Dow Corning, General Electric,Union Carbide, Wacker Chemie, Shin Etsu, Toshiba, Toyo Beauty Co, andToray Silicone Co.

67. The viscosity of the silicone itself (not the emulsion or the finalshampoo composition) is typically at least 10,000 cst. in general wehave found that conditioning performance increases with increasedviscosity. Accordingly, the viscosity of the silicone itself ispreferably at least 60,000 cst, most preferably at least 500,000 cst,ideally at least 1,000,000 cst. Preferably the viscosity does not exceed10⁹ cst for ease of formulation. Viscosity can be measured by means of aglass capillary viscometer as set out further in Dow Corning CorporateTest Method CTM004 Jul. 20 1970.

68. Examples of suitable pre-formed emulsions include emulsionsDC2-1766, DC2-1784, and microemulsions DC2-1865 and DC2-1870, allavailable from Dow Corning. These are all emulsions/microemulsions ofdimethiconol. DC2-1760 and DC2-1784 each have an average siliconeparticle size in the emulsion of less than 2 microns. DC2-1805 andDC2-1870 each have an average silicone particle size in themicroemulsion of less than 0.15 microns. Cross-linked silicone gums arealso available in a pre-emulsified form, which is advantageous for easeof formulation. A preferred example is the material available from DowCorning as DC X2-1787, which is an emulsion of cross-linked dimethiconolgum having an average silicone particle size in the emulsion of 0.5microns. A further preferred example is the material available from DowCorning as DC X2-1391, which is a microemulsion of cross-linkeddimethiconol gum having an average silicone particle size in themicroemulsion of 0.045 microns.

69. Silicone Ratios

70. We have found that the conditioning performance of small particlesize emulsified silicone in a surfactant-based shampoo composition canbe significantly boosted by the presence of an amino functionalisedsilicone.

71. The weight ratio of amino functionalised silicone to non-aminofunctionalised silicone is generally 1:2 or less. Suitably, the ratio ofamino functionalised silicone to non-amino functionalised siliconeranges from 1:2 to 1:20, preferably 1:3 to 1:20, more preferably 1:3 to1:8, optimally around 1:4.

72. Silicone Levels

73. The total amount of silicone (amino functional and non-aminofunctional) incorporated into the shampoo compositions of the inventiondepends on the level of conditioning desired and the material used. Apreferred amount is from 0.01 to about 10% by weight of the totalcomposition although these limits are not absolute. The lower limit isdetermined by the minimum level to achieve conditioning and the upperlimit by the maximum level to avoid making the hair and/or skinunacceptably greasy.

74. We have found that a total amount of silicone of from 0.3 to 5%,preferably 0.5 to 3%, by weight of the total composition is a suitablelevel.

75. Cationic Deposition Polymer

76. A cationic deposition polymer is a preferred ingredient in shampoocompositions of the invention, for enhancing conditioning performance ofthe shampoo. By “deposition polymer” is meant an agent which enhancesdeposition of the silicone component from the shampoo composition ontothe intended site during use, i.e. the hair and/or the scalp.

77. The deposition polymer may be a homopolymer or be formed from two ormore types of monomers. The molecular weight of the polymer willgenerally be between 5 000 and 10 000 000, typically at least 10 000 andpreferably in the range 100 000 to about 2 000 000. The polymers willhave cationic nitrogen containing groups such as quaternary ammonium orprotonated amino groups, or a mixture thereof.

78. The cationic nitrogen-containing group will generally be present asa substituent on a fraction of the total monomer units of the depositionpolymer. Thus when the polymer is not a homopolymer it can containspacer non-cationic monomer units. Such polymers are described in theCTFA Cosmetic Ingredient Directory, 3rd edition. The ratio of thecationic to non-cationic monomer units is selected to give a polymerhaving a cationic charge density in the required range.

79. Suitable cationic deposition polymers include, for example,copolymers of vinyl monomers having cationic amine or quaternaryammonium functionalities with water soluble spacer monomers such as(meth)acrylamide, alkyl and dialkyl (meth)acrylamides, alkyl(meth)acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyl anddialkyl substituted monomers preferably have C1-C7 alkyl groups, morepreferably C1-3 alkyl groups. Other suitable spacers include vinylesters, vinyl alcohol, maleic anhydride, propylene glycol and ethyleneglycol.

80. The cationic amines can be primary, secondary or tertiary amines,depending upon the particular species and the pH of the composition. Ingeneral secondary and tertiary amines, especially tertiary, arepreferred.

81. Amine substituted vinyl monomers and amines can be polymerized inthe amine form and then converted to ammonium by quaternization.

82. The cationic deposition polymers can comprise mixtures of monomerunits derived from amine- and/or quaternary ammonium-substituted monomerand/or compatible spacer monomers.

83. Suitable cationic deposition polymers include, for example:

84. copolymers of 1-vinyl-2-pyrrolidine and 1-vinyl-3-methylimidazoliumsalt (e.g. chloride salt), referred to in the industry by the Cosmetic,Toiletry, and Fragrance Association, (CTFA) as Polyquaternium-16. Thismaterial is commercially available from BASF Wyandotte Corp.(Parsippany, N.J., USA) under the LUVIQUAT tradename (e.g. LUVIQUAT FC370);

85. copolymers of 1-vinyl-2-pyrrolidine and dimethylaminoethylmethacrylate, referred to in the industry (CTFA) as Polyquaternium-11.This material is available commercially from Gaf Corporation (Wayne,N.J., USA) under the GAFQUAT tradename (e.g., GAFQUAT 755N);

86. cationic diallyl quaternary ammonium-containing polymers including,for example, dimethyldiallyammonium chloride homopolymer and copolymersof acrylamide and dimethyldiallylammonium chloride, referred to in theindustry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively;

87. mineral acid salts of amino-alkyl esters of homo-and copolymers ofunsaturated carboxylic acids having from 3 to 5 carbon atoms, (asdescribed in U.S. Pat. No. 4,009,256);

88. cationic polyacrylamides(as described in WO95/22311). Other cationicdeposition polymers that can be used include cationic polysaccharidepolymers, such as cationic cellulose derivatives, cationic starchderivatives, and cationic guar gum gerivatives.

89. Cationic polysaccharide polymers suitable for use in compositions ofthe invention include those of the formula:

A—O—[R—N⁺(R¹)(R²)(R³)X⁻],

90. wherein: A is an anhydroglucose residual group, such as a starch orcellulose anhydroglucose residual. R is an alkylene, oxyalkylene,polyoxyalkylene, or hydroxyalkylene group, or combination thereof. R¹,R² and R³ independently represent alkyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18carbon atoms. The total number of carbon atoms for each cationic moiety(i.e., the sum of carbon atoms in R¹, R² and R³) is preferably about 20or less, and X is an anionic counterion.

91. Cationic cellulose is available from Amerchol Corp. (Edison, N.J.,USA) in their Polymer JR (trade mark) and LR (trade mark) series ofpolymers, as salts of hydroxyethyl cellulose reacted with trimethylammonium substituted epoxide, referred to in the industry (CTFA) asPolyquaternium 10. Another type of cationic cellulose includes thepolymeric quaternary ammonium salts of hydroxyethyl cellulose reactedwith lauryl dimethyl ammonium-substituted epoxide, referred to in theindustry (CTFA) as Polyquaternium 24. These materials are available fromAmerchol Corp. (Edison, N.J., USA) under the tradename Polymer LM-200.

92. Other suitable cationic polysaccharide polymers include quaternarynitrogen-containing cellulose ethers (e.g. as described in U.S. Pat. No.3,962,418), and copolymers of etherified cellulose and starch (e.g. asdescribed in U.S. Pat. No. 3,958,581).

93. A particularly suitable type of cationic polysaccharide polymer thatcan be used is a cationic guar gum derivative, such as guarhydroxypropyltrimonium chloride (Commercially available from Rhodia(formerly Rhone-Poulenc) in their JAGUAR trademark series).

94. Examples are JAGUAR C13S and JAGUAR C3289, which have a low degreeof substitution of the cationic groups and high viscosity. JAGUAR C15,having a moderate degree of substitution and a low viscosity, JAGUAR C17(high degree of substitution, high viscosity), JAGUAR C16, which is ahydroxypropylated cationic guar derivative containing a low level ofsubstituent groups as well as cationic quaternary ammonium groups, andJAGUAR 162 which is a high transparency, medium viscosity guar having alow degree of substitution.

95. Preferably the cationic deposition polymer is selected from cationiccellulose and cationic guar derivatives. Particularly preferreddeposition polymers are JAGUAR C13S, JAGUAR CB289, JAGUAR C15, JAGUARC17 and JAGUAR C16 and JAGUAR C162.

96. The cationic deposition polymer will generally be present at levelsof from 0.001 to 5%, preferably from about 0.01 to 1%, more preferablyfrom about 0.02% to about 0.5% by weight of the total composition.

97. Other Ingredients

98. The shampoo composition of the invention may further comprise from0.1 to 5% by weight of the total composition of a silicone suspendingagent. Examples are polyacrylic acids, cross linked polymers of acrylicacid, copolymers of acrylic acid with a hydrophobic monomer, copolymersof carboxylic acid- containing monomers and acrylic esters, cross-linkedcopolymers of acrylic acid and acrylate esters, heteropolysaccharidegums and crystalline long chain acyl derivatives. The long chain acylderivative is desirably selected from ethylene glycol stearate,alkanolamides of fatty acids having from 16 to 22 carbon atoms andmixtures thereof. Ethylene glycol distearate and polyethylene glycol 3distearate are preferred long chain acyl derivatives. Polyacrylic acidis available commercially as Carbopol 420, Carbopol 488 or Carbopol 493.Polymers of acrylic acid cross-linked with a polyfunctional agent mayalso be used, they are available commercially as Carbopol 910, Carbopol934, Carbopol 940, Carbopol 941 and Carbopol 980. An example of asuitable copolymer of a carboxylic acid containing a monomer and acrylicacid esters is Carbopol 1342. All Carbopol materials are available fromGoodrich and Carbopol is a trade mark.

99. Suitable cross linked polymers of acrylic acid and acrylate estersare Pemulen TR1 or Pemulen TR2. A suitable heteropolysaccharide gum isxanthan gum, for example that available as Kelzan mu.

100. Compositions of this invention may contain any other ingredientnormally used in hair treatment formulations. These other ingredientsmay include viscosity modifiers, preservatives, colouring agents,polyols such as glycerine and polypropylene glycol, chelating agentssuch as EDTA, antioxidants, fragrances, and sunscreens. Each of theseingredients will be present in an amount effective to accomplish itspurpose. Generally these optional ingredients are included individuallyat a level of up to about 5% by weight of the total composition.

101. Preferably, compositions of this invention also contain adjuvantssuitable for hair care. Generally such ingredients are includedindividually at a level of up to 2%, preferably up to 1%, by weight ofthe total composition.

102. Among suitable hair care adjuvants, are:

103. (i) natural hair root nutrients, such as amino acids and sugars.Examples of suitable amino acids include arginine, cysteine, glutamine,glutamic acid, isoleucine, leucine, methionine, serine and valine,and/or precursors and derivatives thereof. The amino acids may be addedsingly, in mixtures, or in the form of peptides, e.g. di- andtripeptides. The amino acids may also be added in the form of a proteinhydrolysate, such as a keratin or collagen hydrolysate. Suitable sugarsare glucose, dextrose and fructose. These may be added singly or in theform of, e.g. fruit extracts. A particularly preferred combination ofnatural hair root nutrients for inclusion in compositions of theinvention is isoleucine and glucose. A particularly preferred amino acidnutrient is arginine.

104. (ii) hair fibre benefit agents. Examples are:

105. ceramides, for moisturising the fibre and maintaining cuticleintegrity. Ceramides are available by extraction from natural sources,or as synthetic ceramides and pseudoceramides. A preferred ceramide isCeramide II, ex Quest. Mixtures of ceramides may also be suitable, suchas Ceramides LS, ex Laboratoires Serobiologiques.

106. The invention is further illustrated by way of the followingnon-limitative Examples:

EXAMPLES Example 1

107. A shampoo composition was prepared by mixing the followingcomponents in the amounts stated: Ingredient % wt Sodium lauryl sulphate(2EO) 14.0 Cocamidopropyl betaine 2.0 Non-amino functionalisedsilicone⁽¹⁾ 1.5 Sodium chloride 1.5 Amino functionalised silicone⁽²⁾ 0.5Carbopol 980⁽³⁾ 0.4 Jaguar C13S⁽⁴⁾ 0.1 Preservative, perfume, q.s.colour Water      to 100.0

Example 2 and Comparative Example A

108. Two shampoo compositions were made up having ingredients as shown %weight in the following Comparative Table: INGREDIENT Example A Example2 Sodium lauryl ether 14.0 14.0 sulphate (2EO Cocamidopropyl 2.0 2.0betaine Jaguar C13S 0.1 0.1 Pearliser⁽⁵⁾ 6.0 6.0 Formalin 0.1 0.1 DC949⁽⁶⁾ 1.0 1.0 DC 200 (60,000 cst)⁽⁷⁾ 2.0 — X2-1766⁽⁸⁾ — 2.0 NaCl 0.90.9 H₂O to 100 to 100

109. The shampoos of Example 2 and Comparative Example A were subjectedto a panellist evaluation for various wet and dry conditioningattributes. The panellist preferences are shown in the following Table:Attribute Example 2 Comparative Example A WET FEEL smoothness 79 21 easeof comb 83 17 DRY FEEL smoothness 75 25 ease of comb 83 17 lack offly-away 85 15

110. Clearly the composition of the invention (with small particle sizesilicone and amino functionalised silicone) outperformed the compositionof the Comparative Example over all attributes tested.

1. An aqueous shampoo composition comprising, in addition to water: i)at least one surfactant chosen from anionic, nonionic, zwitterionic oramphoteric surfactants or mixtures thereof; ii) an amino functionalisedsilicone; and iii) emulsified particles of an insoluble, non-aminofunctionalised silicone, in which the emulsified non-amino functionalsilicone has an average silicone particle size in the shampoocomposition of less than 2 microns.
 2. A shampoo composition accordingto claim 1 , in which the emulsified non-amino functional silicone hasan average silicone particle size in the shampoo composition of from0.01 to 1 micron.
 3. A shampoo composition according to claim 1 or claim2 , in which the weight ratio of amino functionalised silicone (ii) tonon-amino functionalised silicone (iii) is 1:2 or less.
 4. A shampoocomposition according to any preceding claim, in which the aminofunctional silicone has a mole % amine functionality in the range offrom about 0.1 to about 8.0 mole %, preferably from about 0.1 to about5.0 mole %, most preferably from about 0.1 to about 2.0 mole %.
 5. Ashampoo composition according to any preceding claim, in which the aminofunctional silicone is in the form of an emulsion of amino functionalsilicone oil with non ionic and/or cationic surfactant, and in which theaverage particle size of the amino functional silicone in the shampoocomposition is less than 2 microns.
 6. A shampoo composition accordingto any preceding claim, in which the emulsified non-amino functionalsilicone has a viscosity (of the silicone itself) of at least 500,000cst.
 7. A shampoo composition according to any preceding claim, in whichthe total amount of silicone is from 0.3 to 5%, preferably 0.5 to 3%, byweight of the total shampoo composition.
 8. A shampoo compositionaccording to any preceding claim, further comprising from 0.001 to 5% byweight of the total shampoo composition of a cationic deposition polymerselected from cationic cellulose and cationic guar derivatives.